Use of metal complex compounds as oxidation catalysts

ABSTRACT

Use of metal complex compounds of formula (1): [L n Me m X p ] z Y q  wherein Me is manganese, titanium, iron, cobalt, nickel or copper, X is a coordinating or bridging radical, n and m are each independently of the other an integer having a value of from 1 to 8, p is an integer having a value of from 0 to 32, z is the charge of the metal complex, y is a counter-ion, q=z/(charge Y), and L is a ligand of formula (2) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10  and R 11  are each independently of the others hydrogen; unsubstituted or substituted C 1 -C 18 alkyl or aryl; cyano; halogen; nitro; —COOR 12  or —SO 3 R 12  wherein R 12  is in each case hydrogen, a cation or unsubstituted or substituted C 1 -C 18 alkyl or aryl; —SR 13 , —OR 13  or —OR 13  wherein R 13  is in each case hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl; —N(R 13 )—NR′ 13 R″ 13  wherein R 13 , R′ 13  and R″ 13  are as defined above for R 13 ; —NR 14 R 15  or —N + R 14 R 15 R 16  wherein R 14 , R 15  and R 16  are each independently of the other(s) hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl, or R 14  and R 15  together with the nitrogen atom bonding them form an unsubstituted or substituted  5 -,  6 - or  7 -membered ring which may optionally contain further hetero atoms; with the proviso that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  are not simultaneously hydrogen, as catalysts for oxidation reactions, and the novel metal complex compounds of formula (1) and the novel ligands of formula (2).

[0001] The present invention relates to the use of metal complexcompounds with terpyridine ligands as oxidation catalysts. The presentinvention relates also to formulations comprising such metal complexcompounds, to novel metal complex compounds and to novel ligands.

[0002] The metal complex compounds are used especially for improving theaction of peroxides, for example in the treatment of textile material,without at the same time causing any appreciable damage to fibres anddyeings.

[0003] Peroxide-containing bleaching agents have been used in washingand cleaning processes for some time. They have an excellent action at aliquor temperature of 90° C. and above, but their performance noticeablydecreases with lower temperatures. It is known that various transitionmetal ions, added in the form of suitable salts, or coordinationcompounds containing such cations catalyse the decomposition of H₂O₂. Inthat way it is possible to increase the bleaching action of H₂O₂, or ofprecursors that release H₂O₂, or of other peroxo compounds, thebleaching action of which is unsatisfactory at lower temperatures.Particularly significant for practical purposes are those combinationsof transition metal ions and ligands the peroxide activation of which ismanifested in an increased tendency towards oxidation in respect ofsubstrates and not only in a catalase-like disproportionation. Thelatter activation, which tends rather to be undesirable in the presentcase, could impair the bleaching effects of H₂O₂ and its derivativeswhich are insufficient at low temperatures.

[0004] In respect of H₂O₂ activation having effective bleaching action,mononuclear and polynuclear variants of manganese complexes with variousligands, especially with 1,4,7-trimethyl-1,4,7-triazacyclononane andoptionally oxygen-containing bridge ligands, are currently regarded asbeing especially effective. Such catalysts have adequate stability underpractical conditions and, with Mn^(n+), contain an ecologicallyacceptable metal cation, but their use is unfortunately associated withconsiderable damage to dyes and fibres.

[0005] The aim of the present invention was, therefore, to provideimproved metal complex catalysts for oxidation processes which fulfilthe above demands and, especially, improve the action of peroxycompounds in an extremely wide range of fields of use without givingrise to any appreciable damage.

[0006] The invention accordingly relates to the use of metal complexcompounds of formula

[L _(n) Me _(m) X _(p)]^(z) Y _(q)  (1),

[0007] wherein

[0008] Me is manganese, titanium, iron, cobalt, nickel or copper,

[0009] X is a coordinating or bridging radical,

[0010] n and m are each independently of the other an integer having avalue of from 1 to 8,

[0011] p is an integer having a value of from 0 to 32,

[0012] z is the charge of the metal complex,

[0013] Y is a counter-ion,

[0014] q=z/(charge Y), and

[0015] L is a ligand of formula

[0016]  wherein

[0017] R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁, are eachindependently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or aryl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ whereinR₁₂ is in each case hydrogen, a cation or unsubstituted or substitutedC₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each casehydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or substituted 5-, 6- or 7-memberedring which may optionally contain further hetero atoms;

[0018] with the proviso that R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ andR₁₁, are not simultaneously hydrogen,

[0019] as catalysts for oxidation reactions.

[0020] The mentioned C₁-C₁₈alkyl radicals are generally, for example,straight-chain or branched alkyl radicals, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl. Preference isgiven to C₁-C₁₂alkyl radicals, especially C₁-C₈alkyl radicals and moreespecially C₁-C₄alkyl radicals. The mentioned alkyl radicals can beunsubstituted or substituted e.g. by hydroxyl, C₁-C₄alkoxy, sulfo or bysulfato, especially by hydroxyl. The corresponding unsubstituted alkylradicals are preferred. Very special preference is given to methyl andethyl, especially methyl.

[0021] Examples of aryl radicals that generally come into considerationare phenyl or naphthyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthoxy. Preferred substituents are C₁-C₄alkyl,C₁-C₄alkoxy, phenyl and hydroxy. Special preference is given to thecorresponding phenyl radicals.

[0022] Halogen is generally especially chlorine, bromine or fluorine,special preference being given to chlorine.

[0023] Examples of cations that generally come into consideration arealkali metal cations, such as lithium, potassium and especially sodium,alkaline earth metal cations, such as magnesium and calcium, andammonium cations. The corresponding alkali metal cations, especiallysodium, are preferred.

[0024] Suitable metal ions for Me are e.g. manganese in oxidation statesII-V, titanium in oxidation states III and IV, iron in oxidation statesI to IV, cobalt in oxidation states I to III, nickel in oxidation statesI to III and copper in oxidation states I to II, with special preferencebeing given to manganese, especially manganese in oxidation states II toIV, preferably in oxidation state II. Also of interest are titanium IV,iron II-IV, cobalt II-III, nickel II-III and copper II-III, especiallyiron II-IV.

[0025] For the radical X there come into consideration, for example,CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ²⁻, O₂ ⁻, R₁₇COO⁻, R₁₇O⁻, LMeO⁻ andLMeOO⁻, wherein R₁₇ is hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl, and C₁-C₁₈alkyl, aryl, L and Me have thedefinitions and preferred meanings given hereinabove and hereinbelow.R₁₇ is especially hydrogen, C₁-C₄alkyl or phenyl, more especiallyhydrogen.

[0026] As counter-ion Y there come into consideration, for example,R₁₇COO⁻, ClO⁻, BF₄ ⁻, PF₆ ⁻, R₁₇SO₃ ⁻, R₁₇SO₄ ⁻, SO₄ ²⁻, NO₃ ⁻F⁻Cl⁻Br⁻and I⁻, wherein R₁₇ is hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl. R₁₇ as C₁-C₁₈alkyl or aryl has the definitions andpreferred meanings given hereinabove and hereinbelow. R₁₇ is especiallyhydrogen, C₁-C₄alkyl or phenyl, more especially hydrogen. The charge ofthe counter-ion Y is accordingly preferably 1- or 2-, especially 1-.

[0027] n is preferably an integer having a value of from 1 to 4,preferably 1 or 2 and especially 1.

[0028] m is preferably an integer having a value of 1 or 2, especially1.

[0029] p is preferably an integer having a value of from 0 to 4,especially 2.

[0030] z is preferably an integer having a value of from 8− to 8+,especially from 4− to 4+ and more especially from 0 to 4+. z is moreespecially the number 0.

[0031] q is preferably an integer from 0 to 8, especially from 0 to 4and is more especially the number 0.

[0032] R₁₂ is preferably hydrogen, a cation, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above. R₁₂ is especiallyhydrogen, an alkali metal cation, alkaline earth metal cation orammonium cation, C₁-C₄alkyl or phenyl, more especially hydrogen or analkali metal cation, alkaline earth metal cation or ammonium cation.

[0033] R₁₃, R′₁₃ and R″₁₃ are preferably hydrogen, C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above. R₁₃, R′₁₃ andR″₁₃ are especially hydrogen, C₁-C₄alkyl or phenyl, more especiallyhydrogen or C₁-C₄alkyl, preferably hydrogen. Examples of the radical ofthe formula —N(R₁₃)—NR′₁₃R″₁₃ that may be mentioned include —N(CH₃)—NH₂and especially —NH—NH₂. Examples of the radical of the formula —OR₁₃that may be mentioned include hydroxyl and C₁-C₄alkoxy, such as methoxyand especially ethoxy.

[0034] When R₁₄ and R₁₅ together with the nitrogen atom bonding themform a 5-, 6- or 7-membered ring it is preferably an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring. The piperazine ring can be substituted by C₁-C₄alkyle.g. at the nitrogen atom not bonded to the phenyl radical. In addition,R₁₄, R₁₅ and R₁₆ are preferably hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above. Special preference is given to hydrogen,unsubstituted or hydroxyl-substituted C₁-C₄alkyl or phenyl, especiallyhydrogen or unsubstituted or hydroxyl-substituted C₁-C₄alkyl, preferablyhydrogen. Examples of the radical of formula —NR₁₄R₁₅ that may bementioned include —NH₂, —NHCH₂CH₂OH, —N(CH₂CH₂OH)₂, —N(CH₃)CH₂CH₂OH, andthe pyrrolidine, piperidine, piperazine, morpholine or azepane ring andalso 4-methyl-piperazin-1-yl.

[0035] Preference is given to ligands of formula (2) wherein R₆ is nothydrogen.

[0036] R₆ is preferably C₁-C₁₂alkyl; phenyl unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo,hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; cyano; halogen; nitro;—COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholine or azepane ring.

[0037] R₆ is especially phenyl unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, phenyl or by hydroxyl; cyano; nitro;—COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation,C₁-C₄alkyl or phenyl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in eachcase hydrogen, C₁-C₄alkyl or phenyl; —N(CH₃)—NH₂ or —NH—NH₂; amino;N-mono- or N,N-di-C₁-C₄-alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety; or an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

[0038] R₈ is very especially C₁-C₄alkoxy; hydroxy; phenyl unsubstitutedor substituted by C₁-C₄alkyl, C₁-C₄alkoxy, phenyl or by hydroxy;hydrazino; amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety; or an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

[0039] Especially important as radicals RP are C₁-C₄alkoxy; hydroxy;hydrazino; amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety; or the unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

[0040] Very especially important as radicals R₆ are C₁-C₄alkoxy;hydroxy; N-mono- or N,N-di-C₁-C₄alkylamino substituted by hydroxy in thealkyl moiety; or the unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholine or azepane ring,hydroxyl being of particular interest.

[0041] The preferred meanings indicated above for R₆ apply also to R₁,R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁, but those radicals mayadditionally denote hydrogen.

[0042] In accordance with one embodiment of the present invention, R₁,R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are hydrogen and R₆ is a radicalother than hydrogen having the definitions and preferred meaningsindicated above.

[0043] In accordance with a further embodiment of the present invention,R₁, R₂, R₄, R₅, R₇, R₈, R₁₀ and R₁₁, are hydrogen and R₃, R₆ and R₉ areradicals other than hydrogen having the definitions and preferredmeanings indicated above for R₆.

[0044] Preferred ligands L are those of formula

[0045] wherein R′₃ and R′₉ have the definitions and preferred meaningsindicated above for R₃ and R₉, and R′₆ has the definitions and preferredmeanings indicated above for R₆.

[0046] R′₃, R′₆ and R′₉ are preferably each independently of the othersC₁-C₄alkoxy; hydroxy; phenyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, phenyl or by hydroxy; hydrazino; amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; or an unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring.

[0047] The metal complex compounds of formula (1) are known or can beobtained analogously to known processes. They are obtained in a mannerknown per se by reacting at least one ligand of formula (2) in thedesired molar ratio with a metal compound, especially a metal salt, suchas the chloride, to form the corresponding metal complex. The reactionis carried but, for example, in a solvent, such as water or a loweralcohol, such as ethanol, at a temperature of e.g. from 10 to 60° C.,especially at room temperature.

[0048] Ligands of formula (2) that are substituted by hydroxyl can alsobe formulated as compounds having a pyridone structure in accordancewith the following scheme (illustrated here using the example of aterpyridine substituted by hydroxyl in the 4′-position):

[0049] Their special place within the terpyridine family results fromthe fact that such ligands are capable of being deprotonated and aretherefore able to act as anionic ligands.

[0050] Generally, therefore, hydroxyl-substituted terpyridines are alsoto be understood as including those having a corresponding pyridonestructure.

[0051] The ligands of formula (2) are known or can be prepared in amanner known per se. For that purpose, for example, two parts ofpyridine-2-carboxylic acid ester and one part of acetone can be reactedwith sodium hydride and the intermediate, a 1,3,5-triketone, obtainedafter aqueous working-up can be reacted with ammonium acetate tosynthesise the central pyridine ring. The corresponding pyridonederivatives are obtained, which can be converted into the chlorinecompounds by reaction with a chlorinating agent, such as PCl₅/POCl₃.Reactions of such compounds with amines, if desired in the presence ofan excess of redox-active transition metal salts, such as iron orruthenium, in order to accelerate the substitution, yieldamine-substituted terpyridines. Such preparation processes aredescribed, for example, in J. Chem. Soc., Dalton Trans. 1990, 1405-1409(E. C. Constable et al.) and New. J. Chem. 1992, 16, 855-867.

[0052] It has now been found that for the accelerated substitution ofhalide by amine at the terpyridine structure it is also possible to usecatalytic amounts of non-transition metal salts, such as zinc(II) salts,which considerably simplifies the reaction procedure and working-up.

[0053] The present invention relates also to novel metal complexcompounds of formula

[L _(n) Me _(m) X _(p)]^(z) Y _(q)  (1a),

[0054] wherein

[0055] Me is manganese, titanium, iron, cobalt, nickel or copper,

[0056] X is a coordinating or bridging radical;

[0057] n and m are each independently of the other an integer having avalue of from 1 to 8,

[0058] p is an integer having a value from 0 to 32,

[0059] z is the charge of the metal complex,

[0060] Y is a counter-ion,

[0061] q=z/(charge Y), and

[0062] L is a ligand of formula

[0063]  wherein

[0064] R₆ is unsubstituted or substituted C₁-C₁₈alkyl; cyano; halogen;nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cationor unsubstituted or substituted C₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen or unsubstituted orsubstituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ andR″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or —NR₁₄R₁₆R₁₆ wherein R₁₄,R₁₅ and R₁₆ are each independently of the other(s) hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orsubstituted 5-, 6- or 7-membered ring which may optionally containfurther hetero atoms; and

[0065] R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁, are eachindependently of the others as defined above for R₆ or are hydrogen orunsubstituted or substituted aryl,

[0066] with the proviso that when Me is titanium, iron, cobalt, nickelor copper,

[0067] R₃ and R₉ are not hydrogen and the three radicals R₃, R₆ and R₉do not have identical meanings.

[0068] The definitions and preferred meanings given above for thecompounds of formula (1) apply also to the metal complex compounds offormula (1a).

[0069] The ligand L of the metal complex compounds of formula (1a) isespecially a compound of Formula

[0070] wherein

[0071] R′₆ is C₁-C₁₂alkyl; cyano; halogen; nitro; —COOR₁₂ or —O₃R₁₂wherein R₁₂ is in each case hydrogen, a cation, C₁-C₁₂alkyl, or phenylunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano,nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or bynaphthoxy; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N(R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholino or azepane ring; and

[0072] R′₃ and R′₉ are as defined above or are hydrogen or phenylunsubstituted or substituted as indicated above. The definitions andpreferred meanings indicated above for R′₆ and R′₃ and R′₉ likewiseapply here.

[0073] The present invention relates also to the novel ligands offormula

[0074] wherein

[0075] R₆ is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is ineach case hydrogen, a cation or unsubstituted or substituted C₁-C₁₈alkylor aryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl,or R₁₄ and R₁₅ together with the nitrogen atom bonding them form anunsubstituted or substituted 5-, 6- or 7-membered ring which mayoptionally contain further hetero atoms; and

[0076] R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are eachindependently of the others as defined above for R₆ or are hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl,

[0077] with the proviso that the three radicals R₃, R₆ and R₉ do nothave identical meanings.

[0078] The definitions and preferred meanings indicated above for theligands of formula (2) also apply here.

[0079] Preference is given to ligands of formula

[0080] wherein

[0081] R′₆ is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ isin each case hydrogen, a cation, C₁-C₁₂alkyl, or phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl,sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen, unsubstituted or hydroxyl-substituted C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring; and

[0082] R′₃ and R′₉ are as defined above or are hydrogen, C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above. The definitionsand preferred meanings indicated above for R′₆ and R′₃ and R′₉ for theligands of the metal complex compounds of formula (1) likewise applyhere.

[0083] The metal complex compounds of formula (1) are preferably usedtogether with peroxy compounds. Examples that may be mentioned in thatregard include the following uses:

[0084] a) the bleaching of spots or stains on textile material in thecontext of a washing process;

[0085] b) the prevention of redeposition of migrating dyes during thewashing of textile material;

[0086] c) the cleaning of hard surfaces, especially table- andkitchen-ware or glass;

[0087] d) the cleaning of hard surfaces, especially wall tiles or floortiles, more especially for removing mold stains;

[0088] e) use in washing and cleaning solutions having an antibacterialaction;

[0089] f) as pretreatment agents for bleaching textiles;

[0090] g) as catalysts in selective oxidation reactions in the contextof organic synthesis.

[0091] A further use relates to the use of the metal complex compoundsof formula (1) as catalysts for reactions with peroxy compounds forbleaching in the context of paper-making. This relates especially to thebleaching of pulp, which can be carried out in accordance with customaryprocesses. Also of interest is the use of the metal complex compounds offormula (1) as catalysts for reactions with peroxy compounds for thebleaching of waste printed paper.

[0092] Preference is given to the bleaching of spots or stains ontextile material, the prevention of the redeposition of migrating dyesin the context of a washing process, or the cleaning of hard surfaces,especially table- or kitchen-ware or glass. For those purposes it ispreferable to use aqueous formulations of the metal complex compounds offormula (1).

[0093] It should be emphasised that the metal complex compounds do notcause any appreciable damage to fibres and dyeings, for example in thebleaching of textile material.

[0094] Processes for preventing the redeposition of migrating dyes in awashing liquor are usually carried out by adding to the washing liquor,which contains a peroxide-containing washing agent, one or more metalcomplex compounds of formula (1) in an amount of from 0.1, to 200 mg,preferably from 1 to 75 mg, especially from 3 to 50 mg, per litre ofwashing liquor. It will be understood that in such an application, aswell as in the other applications, the metal complex compounds offormula (1) can alternatively be formed in situ, the metal salt (e.g.manganese(II) salt, such as manganese(II) chloride) and the ligand beingadded in the desired molar ratios.

[0095] The present invention relates also to a washing, cleaning,disinfecting or bleaching agent, containing

[0096] I) 0-50%, preferably 0-30%, A) of an anionic surfactant and/or B)of a non-ionic surfactant,

[0097] II) 0-70%, preferably 0-50%, C) of a builder substance,

[0098] III) 1-99%, preferably 1-50%, D) of a peroxide or aperoxide-forming substance, and

[0099] IV) E) a metal complex compound of formula (1) in an amountwhich, in the liquor, gives a concentration of 0.5-50 mg/litre ofliquor, preferably 1-30 mg/litre of liquor, when from 0.5 to 20 g/litreof the washing, cleaning, disinfecting and bleaching agent are added tothe liquor.

[0100] The above percentages are in each case percentages by weight,based on the total weight of the agent. The agents preferably containfrom 0.005 to 2% of a metal complex compound of formula (1), especiallyfrom 0.01 to 1% and preferably from 0.05 to 1%.

[0101] When the agents according to the invention comprise a componentA) and/or B), the amount thereof is preferably 1-50%, especially 1-30%.

[0102] When the agents according to the invention comprise a componentC), the amount thereof is preferably 1-70%, especially 1-50%. Specialpreference is given to an amount of from 5 to 50% and especially anamount of from 10 to 50%.

[0103] Corresponding washing, cleaning, disinfecting or bleachingprocesses are usually carried out by using an aqueous liquor comprisinga peroxide and from 0.1 to 200 mg of one or more compounds of formula(1) per litre of liquor. The liquor preferably contains from 1 to 30 mgof the compound of formula (1) per litre of liquor.

[0104] The agents according to the invention can be, for example, aperoxide-containing complete washing agent or a separate bleachingadditive. A bleaching additive is used for removing coloured stains ontextiles in a separate liquor before the clothes are washed with ableach-free washing agent. A bleaching additive can also be used in aliquor together with a bleach-free washing agent.

[0105] The washing or cleaning agent according to the invention can bein solid or liquid form, for example in the form of a liquid,non-aqueous washing agent, comprising not more than 5% by weight water,preferably comprising from 0 to 1% by weight water, and, as base, asuspension of a builder substance in a non-ionic surfactant, e.g. asdescribed in GB-A-2 158 454.

[0106] The washing or cleaning agent is preferably in the form of apowder or, especially, granules.

[0107] The latter can be prepared, for example, by first preparing aninitial powder by spray-drying an aqueous suspension containing all thecomponents listed above except for components D) and E), and then addingthe dry components D) and E) and mixing everything together.

[0108] It is also possible to add component E) to an aqueous suspensioncontaining components A), B) and C), then to carry out spray-drying andthen to mix component D) with the dry mass.

[0109] It is also possible to start with an aqueous suspension thatcontains components A) and C), but none or only some of component B).The suspension is spray-dried, then component E) is mixed with componentB) and added, and then component D) is mixed in in the dry state.

[0110] It is also possible to mix all the components together in the drystate.

[0111] The anionic surfactant A) can be, for example, a sulfate,sulfonate or carboxylate surfactant or a mixture thereof. Preferredsulfates are those having from 12 to 22 carbon atoms in the alkylradical, optionally in combination with alkyl ethoxysulfates in whichthe alkyl radical has from 10 to 20 carbon atoms.

[0112] Preferred sulfonates are e.g. alkylbenzenesulfonates having from9 to 15 carbon atoms in the alkyl radical. The cation in the case ofanionic surfactants is preferably an alkali metal cation, especiallysodium.

[0113] Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R′¹)—CH₂COOM′¹ wherein R is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R′¹ is C₁-C₄alkyl and M′¹is an alkali metal.

[0114] The non-ionic surfactant B) can be, for example, a condensationproduct of from 3 to 8 mol of ethylene oxide with 1 mol of a primaryalcohol having from 9 to 15 carbon atoms.

[0115] As builder substance C) there come into consideration, forexample, alkali metal phosphates, especially tripolyphosphates,carbonates or hydrogen carbonates, especially their sodium salts,silicates, aluminosilicates, polycarboxylates, polycarboxylic acids,organic phosphonates, aminoalkylenepoly(alkylenephosphonates) ormixtures of those compounds.

[0116] Especially suitable silicates are sodium salts of crystallinelayered silicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

[0117] Among the aluminosilicates, preference is given to thosecommercially available under the names zeolite A, B, X and HS, and alsoto mixtures comprising two or more of those components.

[0118] Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylenediamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

[0119] Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepentamethylenephosphonic acid.

[0120] As the peroxide component D) there come into consideration, forexample, the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 95° C.

[0121] The organic peroxides are, for example, mono- or poly-peroxides,especially organic peracids or salts thereof, such asphthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioicacid, diperoxynonanedibic acid, diperoxydecanedioic acid,diperoxyphthalic acid or salts thereof.

[0122] Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

[0123] The peroxides are added to the agent preferably by mixing thecomponents, for example using a screw metering system and/or a fluidisedbed mixer.

[0124] The agents may comprise, in addition to the combination accordingto the invention, one or more optical brighteners, for example from theclass bis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

[0125] The agent may also comprise suspending agents for dirt, e.g.sodium carboxymethylcellulose, pH regulators, e.g. alkali metal oralkaline earth metal silicates, foam regulators, e.g. soap, salts forregulating the spray-drying and the granulating properties, e.g. sodiumsulfate, perfumes and, optionally, antistatic agents and softeners,enzymes, such as amylase, bleaches, pigments and/or toning agents. Suchconstituents must especially be stable towards the bleaching agent used.

[0126] In addition to the bleach catalyst according to formula (1) it isalso possible to use further transition metal salts or complexes knownas bleach-activating active ingredients and/or conventional bleachactivators, that is to say compounds that, under perhydrolysisconditions, yield unsubstituted or substituted perbenzo- and/orperoxo-carboxylic acids having from 1 to 10 carbon atoms, especiallyfrom 2 to 4 carbon atoms. Suitable bleach activators include thecustomary bleach activators, mentioned at the beginning, that carry O-and/or N-acyl groups having the indicated number of carbon atoms and/orunsubstituted or substituted benzoyl groups. Preference is given topolyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula (4):

[0127] wherein R′₁ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R′₂ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

[0128] Further preferred additives to the agents according to theinvention are polymers which, during the washing of textiles, preventstaining caused by dyes in the washing liquor that have been releasedfrom the textiles under the washing conditions. Such polymers arepreferably polyvinylpyrrolidones or polyvinylpyridine-N-oxides whch mayhave been modified by the incorporation of anionic or cationicsubstituents, especially those having a molecular weight in the range offrom 5000 to 60 000, more especially from 10 000 to 50 000. Suchpolymers are preferably used in an amount of from 0.05 to 5% by weight,especially from 0.2 to 1.7% by weight, based on the total weight of thewashing agent.

[0129] The invention relates also to granules that comprise thecatalysts according to the invention and are suitable for incorporationinto a powder- or granule-form washing, dishwashing, cleaning orbleaching agent. Such granules preferably comprise:

[0130] a) from 1 to 99% by weight, preferably from 1 to 40% by weight,especially from 1 to 30% by weight, of a metal complex compound offormula (1), especially of formula (1a),

[0131] b) from 1 to 99% by weight, preferably from 10 to 99% by weight,especially from 20 to 80% by weight, of a binder,

[0132] c) from 0 to 20% by weight, especially from 1 to 20% by weight,of an encapsulating material,

[0133] d) from 0 to 20% by weight of a further additive and

[0134] e) from 0 to 20% by weight of water.

[0135] As binder (b) there come into consideration anionic dispersants,non-ionic dispersants, polymers and waxes that are water-soluble,dispersible or emulsifiable in water.

[0136] The anionic dispersants used are, for example, commerciallyavailable water-soluble anionic dispersants for dyes, pigments etc.

[0137] The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted-orchlorinated diphenylene or diphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, lignosulfonates or oxylignosulfonatesor heterocyclic polysulfonic acids.

[0138] Especially suitable anionic dispersants are condensation productsof naphthalenesulfonic acids with formaldehyde, sodium salts ofpolymerised organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acids,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethyldiphenyl.

[0139] Suitable non-ionic dispersants are especially compounds having amelting point of, preferably, at least 35° C. that are emulsifiable,dispersible or soluble in water, for example the following compounds:

[0140] 1. fatty alcohols having from 8 to 22 carbon atoms, especiallycetyl alcohol;

[0141] 2. addition products of, preferably, from 2 to 80 mol of alkyleneoxide, especially ethylene oxide, wherein some of the ethylene oxideunits may have been replaced by substituted epoxides, such as styreneoxide and/or propylene oxide, with higher unsaturated or saturatedmonoalcohols, fatty acids, fatty amines or fatty amides having from 8 to22 carbon atoms or with benzyl alcohols, phenyl phenols, benzyl phenolsor alkyl phenols, the alkyl radicals of which have at least 4 carbonatoms;

[0142] 3. alkylene oxide, especially propylene oxide, condensationproducts (block polymers);

[0143] 4. ethylene oxide/propylene oxide adducts with diamines,especially ethylenediamine;

[0144] 5. reaction products of a fatty acid having from 8 to 22 carbonatoms and a primary or secondary amine having at least one hydroxy-loweralkyl or lower alkoxy-lower alkyl group, or alkylene oxide additionproducts of such hydroxyalkyl-group-containing reaction products;

[0145] 6. sorbitan esters, preferably with long-chain ester groups, orethoxylated sorbitan esters, such as polyoxyethylene sorbitanmonolaurate having from 4 to 10 ethylene oxide units or polyoxyethylenesorbitan trioleate having from 4 to 20 ethylene oxide units;

[0146] 7. addition products of propylene oxide with a tri- tohexa-hydric aliphatic alcohol having from 3 to 6 carbon atoms, e.g.glycerol or pentaerythritol; and

[0147] 8. fatty alcohol polyglycol mixed ethers, especially additionproducts of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol ofpropylene oxide with aliphatic monoalcohols having from 8 to 22 carbonatoms.

[0148] Especially suitable non-ionic dispersants are surfactants offormula

R′₁₁—O-(alkylene-O)_(n)—R′₁₂  (5),

[0149] wherein

[0150] R′₁₁ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;

[0151] R′₁₂ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having atleast 6 carbon atoms; or benzyl;

[0152] “alkylene” is an alkylene radical having from 2 to 4 carbon atomsand

[0153] n is a number from 1 to 60.

[0154] A substituent R′₁₁ or R′₁₂ in formula (5) is advantageously thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched. R′₁₁ and R′₁₂ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms.

[0155] Aliphatic saturated monoalcohols that come into considerationinclude natural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetylalcohol or stearyl alcohol, and also synthetic alcohols, e.g.2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononylalcohol, trimethylhexanol, trimethylnonyl alcohol, decanol,C₉-C₁₁oxo-alcohol, tridecyl alcohol, isotridecyl alcohol and linearprimary alcohols (Alfols) having from 8 to 22 carbon atoms. Someexamples of such Alfols are Alfol (8-10), Alfol (9-11), Alfol (10-14),Alfol (12-13) and Alfol (16-18). (“Alfol” is a registered trade mark).

[0156] Unsaturated aliphatic monoalcohols are, for example, dodecenylalcohol, hexadecenyl alcohol and oleyl alcohol.

[0157] The alcohol radicals may be present singly or in the form ofmixtures of two or more components, e.g. mixtures of alkyl and/oralkenyl groups that are derived from soybean fatty acids, palm kernelfatty acids or tallow oils.

[0158] (Alkylene-O) chains are preferably divalent radicals of theformulae

[0159] —(CH₂—CH₂—O)—,

[0160] Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyland preferably cyclohexyl.

[0161] As non-ionic dispersants there come into consideration especiallysurfactants of formula

[0162] wherein

[0163] R₁₃ is C₈-C₂₂alkyl;

[0164] R₁₄ is hydrogen or C₁-C₄alkyl;

[0165] Y₁, Y₂, Y₃ and Y₄ are each independently of the others hydrogen,methyl or ethyl;

[0166] n₂ is a number from 0 to 8; and

[0167] n₃ is a number from 2 to 40.

[0168] Further important non-ionic dispersants correspond to formula

[0169] wherein

[0170] R₁₅ is C₉-C₁₄alkyl;

[0171] R₁₆ is C₁-C₄alkyl;

[0172] Y₅, Y₆, Y₇ and Y₈ are each independently of the others hydrogen,methyl or ethyl, one of the radicals Y₅, Y₆ and one of the radicals Y₇,Y₈ always being hydrogen; and

[0173] n₄ and n₅ are each independently of the other an integer from 4to 8.

[0174] The non-ionic dispersants of formulae (5) to (7) can be used inthe form of mixtures. For example, as surfactant mixtures there comeinto consideration non-end-group-terminated fatty alcohol ethoxylates offormula (5), e.g. compounds of formula (5) wherein

[0175] R₁₁ is C₈-C₂₂alkyl,

[0176] R₁₂ is hydrogen and

[0177] the alkylene-O chain is the radical —(CH₂—CH₂—O)— and

[0178] also end-group-terminated fatty alcohol ethoxylates of formula(7).

[0179] Examples of non-ionic dispersants of formulae (5), (6) and (7)include reaction products of a C₁₀-C₁₃fatty alcohol, e.g. aC₁₃oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxideand/or butylene oxide or the reaction product of one mol of a C₁₃fattyalcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, itbeing possible for the addition products each to be end-group-terminatedwith C₁-C₄alkyl, preferably methyl or butyl.

[0180] Such dispersants can be used singly or in the form of mixtures oftwo or more dispersants.

[0181] Instead of, or in addition to, the anionic or non-ionicdispersant, the granules according to the invention may comprise awater-soluble organic polymer as binder. Such polymers may be usedsingly or in the form of mixtures of two or more polymers.

[0182] Water-soluble polymers that come into consideration are, forexample, polyethylene glycols, copolymers of ethylene oxide withpropylene oxide, gelatin, polyacrylates, polymethacrylates,polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates,polyvinylimidazoles, polyvinylpyridine-N-oxides, copolymers ofvinylpyrrolidone with long-chain x-olefins, copolymers ofvinylpyrrolidone with vinylimidazole,poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers ofvinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymersof vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymersof vinylcaprolactam/vinylpyrrolidoneldimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolymers ofcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose,polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate,copolymers of ethyl acrylate with methacrylate and methacrylic acid,copolymers of maleic acid with unsaturated hydrocarbons, and also mixedpolymerisation products of the mentioned polymers.

[0183] Of those organic polymers, special preference is given topolyethylene glycols, carboxymethylcellulose, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, copolymers of ethyl acrylate with methacrylate andmethacrylic acid, and polymethacrylates.

[0184] Suitable water-emulsifiable or water-dispersible binders alsoinclude paraffin waxes.

[0185] Encapsulating materials (c) include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and polymethacrylates.

[0186] Further additives (d) that come into consideration are, forexample, wetting agents, dust removers, water-insoluble or water-solubledyes or pigments, and also dissolution accelerators, optical brightenersand sequestering agents.

[0187] The preparation of the granules according to the invention iscarried out, for example, starting from:

[0188] a) a solution or suspension with a subsequent drying/shaping stepor

[0189] b) a suspension of the active ingredient in a melt withsubsequent shaping and solidification.

[0190] a) First of all the anionic or non-ionic dispersant and/or thepolymer and, if appropriate, the further additives are dissolved inwater and stirred, if desired with heating, until a homogeneous solutionhas been obtained. The catalyst according to the invention is thendissolved or suspended in the resulting aqueous solution. The solidscontent of the solution should preferably be at least 30% by weight,especially 40 to 50% by weight, based on the total weight of thesolution. The viscosity of the solution is preferably less than 200mPas.

[0191] The aqueous solution so prepared, comprising the catalystaccording to the invention, is then subjected to a drying step in whichall water, with the exception of a residual amount, is removed, solidparticles (granules) being formed at the same time. Known methods aresuitable for producing the granules from the aqueous solution. Inprinciple, both continuous methods and discontinuous methods aresuitable. Continuous methods are preferred, especially spray-drying andfluidised bed granulation processes.

[0192] Especially suitable are spray-drying processes in which theactive ingredient solution is sprayed into a chamber with circulatinghot air. The atomisation of the solution is effected e.g. using unitaryor binary nozzles or is brought about by the spinning effect of arapidly rotating disc. In order to increase the particle size, thespray-drying process may be combined with an additional agglomeration ofthe liquid particles with solid nuclei in a fluidised bed that forms anintegral part of the chamber (so-called fluid spray). The fine particles(<100 μm) obtained by a conventional spray-drying process may, ifnecessary after being separated from the exhaust gas flow, be fed asnuclei, without further treatment, directly into the atomizing cone ofthe atomiser of the spray-dryer for the purpose of agglomeration withthe liquid droplets of the active ingredient.

[0193] During the granulation step, the water can rapidly be removedfrom the solutions comprising the catalyst according to the invention,binder and further additives. It is expressly intended thatagglomeration of the droplets forming in the atomising cone, or theagglomeration of droplets with solid particles, will take place.

[0194] If necessary, the granules formed in the spray-dryer are removedin a continuous process, for example by a sieving operation. The finesand the oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

[0195] A further preparation method according to a) is a process inwhich the polymer is mixed with water and then the catalyst isdissolved/suspended in the polymer solution, thus forming an aqueousphase, the catalyst according to the invention being homogeneouslydistributed in that phase. At the same time or subsequently, the aqueousphase is dispersed in a water-immiscible liquid in the presence of adispersion stabiliser in order that a stable dispersion is formed. Thewater is then removed from the dispersion by distillation, formingsubstantially dry particles. In those particles, the catalyst ishomogeneously distributed in the polymer matrix.

[0196] The granules according to the invention are wear-resistant, lowin dust, pourable and readily meterable. They can be added directly to aformulation, such as a washing agent formulation, in the desiredconcentration of the catalyst according to the invention.

[0197] Where the coloured appearance of the granules in the washingagent is to be suppressed, this can be achieved, for example, byembedding the granules in a droplet of a whitish meltable substance(“water-soluble wax”) or by adding a white pigment (e.g. TiO₂) to thegranule formulation or, preferably, by encapsulating the granules in amelt consisting, for example, of a water-soluble wax, as described inEP-A-0 323 407, a white solid being added to the melt in order toreinforce the masking effect of the capsule.

[0198] b) The catalyst according to the invention is dried in a separatestep prior to the melt-granulation and, if necessary, dry-ground in amill so that all the solids particles are <50 μm in size. The drying iscarried out in an apparatus customary for the purpose, for example in apaddle dryer, vacuum cabinet or freeze-dryer.

[0199] The finely particulate catalyst is suspended in the moltencarrier material and homogenised. The desired granules are produced fromthe suspension in a shaping step with simultaneous solidification of themelt. The choice of a suitable melt-granulation process is made inaccordance with the desired size of granules. In principle, any processwhich can be used to produce granules in a particle size of from 0.1 to4 mm is suitable. Such processes are droplet processes (withsolidification on a cooling belt or during free fall in cold air),melt-prilling (cooling medium gas/liquid), and flake formation with asubsequent comminution step, the granulation apparatus being operatedcontinuously or discontinuously.

[0200] Where the coloured appearance of the granules prepared from amelt is to be suppressed in the washing agent, in addition to thecatalyst it is also possible to suspend in the melt white or colouredpigments which, after solidification, impart the desired colouredappearance to the granules (e.g. titanium dioxide).

[0201] If desired, the granules can be covered or encapsulated in anencapsulating material.

[0202] Methods suitable for such an encapsulation include the customarymethods and also the encapsulation of the granules by a melt consistinge.g. of a water-soluble wax, as described, for example, in EP-A-0 323407, coacervation, complex coacervation and surface polymerisation.

[0203] Encapsulatng materials (c) include e.g. water-soluble,water-dispersible or water-emulsifiable polymers and waxes.

[0204] Further additives (d) include e.g. wetting agents, dust-removers,water-insoluble or water-soluble dyes or pigments, and also dissolutionaccelerators, optical brighteners and sequestering agents.

[0205] Surprisingly, the metal complex compounds of formula (1) alsoexhibit a markedly improved bleach-catalysing action on coloured stainson hard surfaces. The addition of such complexes in catalytic amounts toa dishwashing agent that comprises a peroxy compound and optionally TAED(N,N,N′,N′-tetraacetylethylenediamine) results in the substantialremoval of e.g. tea stains on china. This is the case even when hardwater is used, it being known that tea deposits are more difficult toremove in hard water than in soft water. The compounds are also verysuitable for cleaning hard surfaces at low temperatures.

[0206] The use of metal complex compounds of formula (1) as catalystsfor reactions with peroxy compounds in cleaning solutions for hardsurfaces, especially for kitchen- and table-ware, is therefore ofspecial interest.

[0207] The present invention relates also to cleaning agents for hardsurfaces, especially cleaning agents for table- and kitchen-ware and,among such agents, preferably those for use in cleaning processescarried out by machine, which agents comprise one of the above-describedmetal complex compounds of formula (1) as bleach catalyst. Suitableformulations for such cleaning agents include, for example, theformulations mentioned above for the washing agents.

[0208] The metal complex compounds of formula (1) also have, togetherwith peroxy compounds, excellent antibacterial action. The use of themetal complex compounds of formula (1) for killing bacteria or forprotecting against bacterial attack is therefore likewise of interest.

[0209] The metal complex compounds of formula (1) are also outstandinglysuitable for selective oxidation in the context of organic synthesis,especially the oxidation of organic molecules, e.g. of olefins to formepoxides. Such selective transformation reactions are requiredespecially in process chemistry. The invention accordingly relates alsoto the use of the metal complex compounds of formula (1) in selectiveoxidation reactions in the context of organic synthesis.

[0210] The following Examples serve to illustrate the invention but donot limit the invention thereto.

[0211] Parts and percentages relate to weight, unless otherwiseindicated.

EXAMPLES

[0212] Synthesis of 4′-Substituted Terpyridines and 4-pyridones

Example 1 1′H-[2,2′;6′,2″]Terpyridin-4′-one (Referred to as L1 Below)

[0213]

[0214] a) Step 1:

[0215] In a nitrogen atmosphere, under reflux, a solution of 20.2 ml(22.7 g, 150 mmol) of pyridine-2-carboxylic acid ethyl ester and 3.6 ml(50 mmol) of dry acetone in 100 ml of dry tetrahydrofuran is added inthe course of 4 hours to a suspension of 6 g (approximately 60%dispersion in paraffin oil, about 150 mmol) of sodium hydride in 100 mlof dry tetrahydrofuran. The mixture is boiled at reflux for a further 2hours and then concentrated using a rotary evaporator. After theaddition of 200 ml of ice-water, the mixture is rendered neutral with50% strength acetic acid and the resulting yellow1,5-di-pyridin-2-yl-pentane-1,3,5-trione is filtered off. IR (cm⁻¹):2953 (s); 2923 (vs); 2854 (m); 1605 (m); 1560 (s); 1447 (w); 1433 (w);1374 (m); 1280 (w); 786 (w).

[0216] b) Step 2:

[0217] A mixture of 10 g (37 mmol) of1,5-di-pyridin-2-yl-pentane-1,3,5-trione and 20 g (260 mmol) of ammoniumacetate is boiled under reflux in 250 ml of ethanol for 8 hours. Themixture so obtained is concentrated to about half its volume. Afterfiltration, 1′H-[2,2′;6′,2″]terpyridine-4′-one is obtained in the formof a white solid. ¹H-NMR (360 MHz, DMSO-d₆): 7.40-7.50 (qm, 2H); 7.87(s, 2H); 7.92-8.0 (tm, 2H); 8.57 (d, 2H, 7.7 Hz); 8.68 (d, 2H, J=4.5Hz), 10.9 (s, 1H). MS (EI pos., 70 eV), m/z=249 (100, [M+]); 221 (40).

[0218] (for preparation see also K. T. Potts, D. Konwar, J. Org. Chem.2000, 56, 4815-4816 and E. C. Constable, M. D. Ward, J. Chem. Soc.Dalton Trans. 1990,1405-1409).

Example 2 4′-Chloro-[2,2′;6′,2″]terpyridine (Referred to as L2 Below)

[0219]

[0220] A mixture of 3.99 g (16 mmol) of1′H-[2,2′;6′,2″]terpyridin-4′-one (L1) and 8.0 g (38 mmol) of phosphoruspentachloride is boiled at reflux in 200 ml of phosphorus oxychloridefor sixteen hours. The mixture is allowed to cool and concentrated todryness. 200 ml of ice-water are then added cautiously to the residue,and the solution is then adjusted to pH 9 with aqueous potassiumhydroxide solution. Extracton is carried out three times usingchloroform and the organic extracts are dried over sodium sulfate,filtered and concentrated. After recrystallisation from ethanol,4′-chloro-[2,2′;6′,2″]terpyridine is obtained in the form of whiteneedles. ¹H-NMR (CDCl₃, 360 MHz): 7.20-7.29 (m, 2H); 7.70-7.79 (tm, 2H);8.37 (s, 2H); 8.47 (d, 2H; 7.6 Hz); 8.56-8.63 (dm, 2H).

[0221] (for preparation see also E. C. Constable, M. D. Ward, J. Chem.Soc. Dalton Trans. 1990, 1405-1409).

Example 3 4′-Ethoxy-[2,2′;6′,2″]terpyridine (Referred to as L3 Below)

[0222]

[0223] In a nitrogen atmosphere, 900 mg (3.4 mmol) of4′-chloro-[2,2′;6′,2″]terpyridine are added to 15 ml of a 0.7M ethanolicsodium ethanolate solution. The mixture is heated at reflux for 20hours. The mixture is allowed to cool and 20 ml of water are added, and4′-ethoxy-[2,2′;6′,2″]terpyridine is filtered off in the form of a whitesolid. ¹H-NMR (360 MHz, DMSO-d6): 1.40 (t, 3H, 6.8 Hz); 4.28 (q, 2H. 6.8Hz); 7.42-7.53 (m, 2H); 7.93 (s, 2H); 7.95-8.02 (m, 2H); 8.58 (d, 2H,J=8.1 Hz); 8.69 (d, 2H, J=4 Hz).

[0224] (for preparation see also E. C. Constable, A. M. W. CargillThompson, New. J. Chem. 1992, 16, 855-867).

Example 4 [2,2′;6′,2″]Terpyridin-4′-yl-hydrazine (Referred to as L4Below)

[0225] 4 ml (126 mmol) of hydrazine are added to 600 mg (2.2 mmol) of4′-chloro-[2,2′;6′,2″]-terpyridine in 12 ml of 2-butanol. The mixture isheated at reflux for 17 hours and cooled, and[2,2′;6′,2″]terpyridin-4′-yl-hydrazine is filtered off in the form of awhite solid. ¹H-NMR (360 MHz, DMSO-d₆): 4.38 (s br, 2H); 7.38-7.45 (m,2H); 7.84 (s, 2H); 7.88-7.97 (m, 3H); 8.52-8.57 (m, 2H); 8.64-8.76 (m,2H).

[0226] (for preparation see also G. Lowe et al., J. Med. Chem., 1999,42, 999-1006).

Example 5 2-(Methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol(Referred to as L5 Below)

[0227]

[0228] A solution in 20 ml of dichloromethane of 1.61 g (6 mmol) of4′-chloro-2,2′:6′,2″-terpyridine and 20 ml of N-methylaminoethanol areadded in succession to a solution of 1.35 g (6.8 mmol) of iron(II)chloride tetrahydrate in 100 ml of isopropanol. The mixture is thenboiled at reflux for 20 hours. The mixture is concentrated and asolution of 1.66 g of ammonium hexafluorophosphate in 10 ml of methanolis added. The resulting violet precipitate is washed four times using 50ml of diethyl ether each time and once with 50 ml of water. The residueis then stirred for 14 hours in a solution of 4 g of sodium hydroxide in300 ml of water/acetonitrile (1:1 v/v) in an oxygen atmosphere.Filtration is carried out over kieselguhr and the residue is washed with50 ml of water, 50 ml of acetonitrile and 100 ml of dichloromethane. Thefiltrates are concentrated. Extraction is carried out four times withdichloromethane and the combined organic extracts are dried over sodiumsulfate, filtered and concentrated. The residue is recrystallised fromacetone/petroleum ether and acetonitrile;2-(methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol is obtained in theform of a white solid. MS (ESI pos., KF), m/z=345 (100, [M+K]⁺); 307(35, [M+H]⁺).

[0229] (for preparation see also G. Lowe et al., J. Med. Chem., 1999,42, 999-1006).

Example 6 4′-Pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L6Below)

[0230] 28 mg (<5 mol %) of zinc(II) chloride and 4.4 g (61.5 mmol) ofpyrrolidine are added in succession to a mixture of 1.1 g (4;1 mmol) of4′-chloro-[2,2′;6′,2″]terpyridine in 15 ml of 2-methyl-2-butanol. Themixture is heated at reflux for 20 hours, cooled and filtered. Afterrecrystallisation from toluene, pure4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine is obtained in the form of awhite solid. MS (EI, 70 eV): m/z=303 (15); 302 (90, [M+]); 273 (100);233 (25). ¹H-NMR (360 MHz, CDCl₃): 1.9-2.0 (m, 4H); 3.39-3.49 (m, 4H);7.18 (dd, 2H, J=6.7, 5.2 Hz); 7.51 (s, 2H); 7.66-7.76 (tm, 2H); 8.51 (d,2H, J=7.7 Hz); 8.54-8.60 (m, 2H).

Example 72-[(2-Hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol(Referred to as L7 Below)

[0231] 3.41 g (17.2 mmol) of manganese(II) chloride tetrahydrate and 98g (0.93 mol) of diethanolamine are added in succession to a mixture of2.14 g (8 mmol) of 4′-chloro-[2,2′;6′,2″]-terpyridine in 200 ml ofmethanol. The mixture is heated at reflux for 14 hours, cooled andconcentrated. The residue so obtained is stirred in 250 ml of sodiumhydroxide solution in acetonitrile/water 1:1 (v/v, pH>12) for 20 hoursin air. Acetonitrile is removed using a rotary evaporator and theaqueous portion is extracted three times with chloroform. The organicextract is filtered over sodium sulfate and concentrated. Diethyl etheris added to the residue and the mixture is stirred and filtered,yielding2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]-terpyridin-4′-yl-amino]-ethanol in theform of a white solid. ¹H-NMR (360 MHz, CD₃OD): 3.76 (t, J=5.4 Hz, 4H);3.85 (t, J=5.4 Hz, 4H); 7.38-7.47 (tm, 2H); 7.69 (s, 2H); 7.94 (dt,J=8.1, 1.8 Hz, 2H); 8.53 (d, J=8.1 Hz, 2H); 8.58-8.65 (dm, 2H).

Example 8 4′-(4-Methyl-piperazin-1-yl)-[2,2′;6′,2″]terpyridine (Referredto as L8 Below)

[0232]

[0233] This compound is prepared analogously to the procedure indicatedabove for the preparation of the ligand L7 in Example 7, but1-methylpiperazine is used as amine component.4′-(4-Methyl-piperazin-1-yl)-[2,2′;6′,2″]terpyridine, white solid.¹³C-NMR (90 MHz, CDCl₃): 157.1 (2 signals, quart.); 156.3 (quart.);149.1 (tert.); 137.0 (tert.); 123.8 (tert); 121.6 (tert); 105.7 (tert.);55.0 (sec.); 46.6 (sec.); 46.4 (prim.). MS (EI pos., 70 eV), m/z=331(100, [M⁺]), 261 (95); 233 (40); 70 (40); 50 (43).

Example 8b 1,1-Dimethyl-4-[2,2′;6′,2″]terpyridin-4′-yl-piperazin-1-iumiodide (Referred to as L8b Below)

[0234] 211 mg (0.64 mmol) of ligand L8 are dissolved in 11 ml ofacetonitrile and at room temperature an excess of methyl iodide (2.1 ml)is added dropwise thereto. The mixture is then stirred for 3 hours atroom temperature and concentrated, and 10 ml of dichloromethane areadded to the residue. The precipitate is filtered off and dried invacuo, 1,1-dimethyl-4-[2,2′;6′,2″]terpyridin-4′-yl-piperazin-1-iumiodide, beige solid. ¹H-NMR (360 MHz, CD₃OD): 3.34 (s, 6H), 3.62-3.80(m, 4H); 3.85-4.03 (m, 4H); 7.39-7.52 (m, 2H); 7.86-8.03 (m, 4H); 8.57(d, J=7.7 Hz, 2H); 8.63 (d, J=4.5 Hz, 2H).

Example 9 4′-Azepan-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L9Below)

[0235]

[0236] This compound is prepared analogously to the procedure indicatedabove for the preparation of the ligand L7 in Example 7, buthexamethyleneimine is used as amine component.4′-Azepan-1-yl-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR (90 MHz,CDCl₃): 157.7 (quart.); 156.1 (quart.); 155.6 (quart); 149.2 (tert.);137.0 (tert.); 123.7 (tert.); 121.8 (tert); 103.7 (tert); 49.4 (sec);27.9 (sec); 27.4 (sec). MS (EI pos., 70 eV), m/z=330 (100, [M+]); 287(45); 273 (25); 233 (20).

Example 10 4′-Piperidin-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L10Below)

[0237]

[0238] This compound is prepared analogously to the procedure indicatedabove for the preparation of the ligand L7 in Example 7, but piperidineis used as amine component. 4′-Piperidin-1-yl-[2,2′;6′,2″]terpyridine,white solid. ¹³C-NMR (CDCl₃): 157.4 (quart.); 157.3 (quart.); 156.2(quart.); 149.2 (tert.); 137.1 (tert.); 123.8 (tert); 121.8 (tert.);105.7 (tert.); 48.1 (sec.); 25.9 (sec.); 24.9 (sec.). MS (EI pos., 70eV), m/z=316 (100, [M+]); 287 (35); 261 (25); 233 (70).

Example 11 4′-Morpholin-4-yl-[2,2′;6′,2″]terpyridine (Referred to as L11Below)

[0239]

[0240] This compound is prepared analogously to the procedure indicatedabove for the preparation of the ligand L7 in Example 7, but morpholineis used as amine component. 4′-Morpholin-4-yl-[2,2′;6′,2″]terpyridine,white solid. ¹³C-NMR (CDCl₃): 157.6 (quart.); 157.0 (quart.); 156.5(quart.); 149.2 (tert.); 137.2 (tert.); 124.0 (tert.); 121.8 (tert.);105.7 (tert.); 67.0 (sec.); 47.0 (sec.). MS (EI pos., 70 eV), m/z=318(100, [M+]); 287 (35); 261 (45); 233 (85).

Example 12 4′-(4-tert-Butyl-phenyl)-[2,2′;6′,2″]terpyridine (Referred toas L12 Below)

[0241] 4.06 g (25 mmol) of 4-tert-butyl benzaldehyde are dissolved in150 ml of ethanol. Sodium hydroxide solution (5.13 g in 40 ml of water)is added and then 10.54 g (87 mmol) of 2-acetylpyridine are addeddropwise over a period of 10 minutes. The mixture is then stirred atroom temperature for 18 hours. The pale pink precipitate so obtained isfiltered with suction and washed with 10 ml each of methanol and water.A second fraction is obtained from the mother liquor by adding water.2.54 g of the residue so obtained are then taken up in 160 ml of glacialacetic acid; 32 g (excess) of ammonium acetate are added and the mixtureis heated at reflux for 3 hours. The mixture is cooled, neutralised withsodium carbonate solution and extracted twice with dichloromethane. Themixture is dried over sodium sulfate and filtered and the organicextract is concentrated. After recrystallisation from methanol,4′-(4-tert-butyl-phenyl)-[2,2′;6′,2″]terpyridine is obtained in the formof a white solid. ¹³C-NMR (90 MHz, CDCl₃): 156.8 (quart.); 156.3(quart.); 152.7 (quart.); 150.5 (quart.); 149.5 (tert.); 137.2 (tert.);135.9 (quart.); 127.4 (tert.); 126.3 (tert.); 124.1 (tert.); 121.8(tert.); 119.2 (tert.); 35.0 (quart.); 31.6 (prim.).

[0242] (for preparation see also E. C. Constable, P. Harveson, D. R.Smith, L. Whall, Polyhedron 1997,16,3615-3623).

Example 13 4′-(4-Isopropyl-phenyl)-[2,2′;6′,2″]terpyridine (Referred toas L13 Below)

[0243]

[0244] This compound is prepared analogously to the procedure describedabove for the preparation of the ligand L12 in Example 12, but4-isopropyl benzaldehyde is used as carbonyl component.4′-(4-Isopropyl-phenyl)-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 155.4 (quart.); 155.0 (quart.); 149.3 (quart.); 149.1(quart.); 148.2 (tert.); 135.9 (tert.); 135.0 (quart.); 126.4 (tert.);125.8 (tert.); 122.8 (tert.); 120.5 (tert.); 117.6 (tert.); 30.0(tert.); 23.0 (prim.).

Example 14 4′-p-Tolyl-[2,2′;6′,2″]terpyridine (Referred to as L14 Below)

[0245]

[0246] This compound is prepared analogously to the procedure describedabove for the preparation of the ligand L12 in Example 12, but4-methylbenzaldehyde is used as carbonyl component.4′-p-Tolyl-[2,2′;6′,2″]terpyridine, white solid. ³C-NMR (90 MHz, CDCl₃):155.8 (quart.); 155.3 (quart.); 149.6 (quart.); 148.5 (tert.); 138.5(quart.); 136.0 (tert.); 134.9 (quart.); 128.7 (tert.); 126.6 (tert.);123.2 (tert.); 120.8 (tert.); 118.0 (tert.); 20.7 (prim.).

Example 15 4′-Biphenyl-4-yl-[2,2′;6′,2″]terpyridine (Referred to as L15Below)

[0247]

[0248] This compound is prepared analogously to the procedure describedabove for the preparation of the ligand L12 in Example 12, but 4-phenylbenzaldehyde is used as carbonyl component.4′-Biphenylyl-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR (90 MHz,CDCl₃): 156.6 (quart.); 156.3 (quart.); 150.0 (quart.); 149.5 (tert.);142.2 (quart.); 140.8 (quart.); 137.6 (quart.); 136.9 (tert.); 129.3(tert.); 128.1 (tert.); 128.0 (tert.); 127.9 (tert.); 126.3 (tert.);124.2 (tert.); 121.8 (tert.); 119.1 (tert.).

[0249] Synthesis of Building Blocks for Polysubstituted Ligands of thePyridone Type

Example 16 4-Chloro-pyridine-2-carboxylic Acid Methyl Ester

[0250] a) Step 1: 36.9 g (0.3 mol) of pyridine-2-carboxylic acid aredissolved in 105 ml of thionyl chloride. After the addition of 3.1 g (30mmol) of sodium bromide, the mixture is heated cautiously to refluxtemperature. Boiling is continued for 24 hours, the gases formed beingremoved via a wash bottle filled with sodium hydroxide solution. Whenthe reaction is complete, the mixture is allowed to cool andconcentrated using a rotary evaporator.

[0251] b) Step 2:

[0252] 300 ml of methanol are cautiously added, with stirring, at 0° C.to the brown residue obtained in Step 1. The mixture is heated to roomtemperature and stirred for a further 30 minutes to complete thereaction. The mixture is concentrated and 750 ml of 5% strength sodiumhydrogen carbonate solution are added thereto; extraction is carried outthree times using ethyl acetate. The organic extracts are dried oversodium sulfate, filtered and concentrated. The crude product so obtainedis distilled in a sickle flask (about 100-120° C., 0.1 mbar).4-Chloro-pyridine-2-carboxylic acid methyl ester is obtained in the formof a white solid. ¹H-NMR (360 MHz, CDCl₃): 4.01 (s, 3H); 7.44 (dd, 1H,J=5.4, 1.8 Hz); 8.12 (d, 1H, J=1.8 Hz); 8.4 (d, 1H. J=5.4 Hz).

[0253] (for preparation see also R. J. Sundberg, S. Jiang, Org. Prep.Proced. Int. 1997, 29, 117-122).

Example 17 4-Ethoxy-pyridine-2-carboxylic Acid Ethyl Ester

[0254] This compound is obtained in a manner analogous to that describedIn Example 16, except that in Step 2 ethanol is used instead of methanoland the mixture is heated at reflux for 24 hours after the addition ofalcohol. The purification of the crude product is effected bydistillation (100-105° C., 0.08 mbar). 4-Ethoxy-pyridine-2-carboxylicacid ethyl ester is obtained in the form of a colourless oil. ¹H-NMR(360 MHz, CDCl₃): 1.44 (m, 6H); 4.15 (q, 2H, J=7.0 Hz); 4.47 (q, 2H,J=7.0 Hz); 6.94 (dd, 1H, J=5.1, 2.7 Hz); 7.65 (d, 2H, J=2.7 Hz); 8.54(d, 1H; J=5.7 Hz).

Example 18 4-Pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester

[0255] a) Step 1:

[0256] This step is carried out in a manner analogous to that describedin Step 1 in Example 16.

[0257] b) Step 2:

[0258] This step is carried out as described in T. Sammakia, T. B.Hurley, J. Org. Chem. 2000, 65, 974-978: to the resulting crude acidchloride in dichloromethane there is added dropwise at 0° C. adichloromethane solution of a threefold excess of pyrrolidine andcatalytic amounts of N,N-dimethylaminopyridine. The mixture is thenstirred for a further one hour at room temperature, then heated atreflux for 5 hours and concentrated using a rotary evaporator. Theresidue is then extracted five times with diethyl ether. The etherealextracts are concentrated.

[0259] The residue is then taken up in 6M hydrochloric acid and boiledat reflux for 6 hours.

[0260] On concentration using a rotary evaporator, pure4-pyrrolidin-1-yl-pyridine-2-carboxylic acid is precipitated. For thesynthesis of 4-pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester,the carboxylic acid is taken up in thionyl chloride and heated atboiling for 30 minutes. Concentration is carried out using a rotaryevaporator and the procedure is then as described in Example 16, Step 2,except that ethanol is used as alcohol.

Example 19 1,5-Bis(4-chloro-pyridin-2-yl)pentane-1,3,5-trione

[0261]

[0262] This compound is prepared in a manner analogous to that describedin Example 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-chloro-pyridine-2-carboxylic acid methyl ester from Example 16is used. The beige solid crude product is used for further syntheseswithout special purification steps.

[0263] IR (cm⁻¹): 1619 (m); 1564 (s); 1546 (s); 1440 (m); 1374 (s); 1156(m); 822 (w).

Example 20 1,5-Bis(4-ethoxy-pyridin-2-yl)pentane-1,3,5-trione

[0264]

[0265] This compound is prepared in a manner analogous to that describedin Example 1, Step ₁, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-ethoxy-pyridine-2-carboxylic acid ethyl ester from Example 17is used. The yellowish crude product is used for further syntheseswithout special purification steps. IR (cm⁻¹): 1557 (vs); 1469 (w); 1436(w); 1300 (m); 1207 (m); 1186 (m); 1035 (m); 818 (m).

Example 21 1,5-Bis(4-pyrrolidin-1-yl-pyridin-2-yl)-pentane-1,3,5-trione

[0266]

[0267] This compound is prepared in a manner analogous to that describedin Example 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester fromExample 18 is used. The yellow-orange crude product is used for furthersyntheses without special purification steps. IR (cm⁻¹): 1548 (s); 1504(s); 1453 (s); 1381 (s); 1349 (m); 1276 (w); 1243 (M); 1207 (w); 796(w).

[0268] Synthesis of Polysubstituted Terpyridines and Pyridones

Example 22 4,4‘-Dichloro-l’ H-[2,2′;6′,2″]terpyridin-4′-one (Referred toas L16 Below)

[0269]

[0270] This compound is prepared in a manner analogous to that describedin Example 1, Step 2, for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the chloro-substituted triketone from Example 19 is used. Pure4,4″-dichloro-1′H-[2,2′;6′,2″]terpyridin-4′-one can be obtained byrecrystallisation from toluene in the form of a white crystallinepowder. ¹³C-NMR (90 MHz, CDCl₃): 165.6 (quart.); 156.5 (quart.); 154.9(quart.); 150.2 (tert.); 143.6 (quart.); 123.7 (tert.); 120.2 (tert.);108.5 (tert.).

Example 23 4,4″-Diethoxy-1′H-[2,2′;6′,2″⁵]terpyridin-4′-one (Referred toas L17 Below)

[0271]

[0272] This compound is prepared in a manner analogous to that describedin Example 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the ethoxy-substituted triketone from Example 20 is used. Pure4,4″-diethoxy-1′H-[2,2′;6′,2″]terpyridin-4′-one can be obtained bychromatography on silica gel (chloroform/methanol 9:1, 0.1% NH₄OH) inthe form of a white crystalline powder. ¹H-NMR (360 MHz, CDCl₃): 1.37(t, 6H, 7.2 Hz); 4.05 (q, 4H, 7.2 Hz); 6.77 (dd, 2H, J=5.9, 2.3 Hz),6.99 (br s, 2H), 7.30 (br s, 2H); 8.42 (d, 2H, J=5.9 Hz).

[0273] MS (EI pos., 70 eV), m/z=337 (75, [M+]); 322 (90); 309 (100); 281(75); 28 (85).

Example 24 4,4″-Di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one(Referred to as L18 Below)

[0274]

[0275] This compound is prepared in a manner analogous to that describedin Example 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the pyrrolidine-substituted triketone from Example 21 is used.Pure 4,4″-di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one can beobtained by recrystallisation from methanol in the form of an almostcolourless solid. 1.81-2.05 (m, 8H); 3.17-3.33 (m, 8H); 6.32 (dd, 2H,J=5.7, 2.3 Hz); 6.84 (d, 2H, J=2.3 Hz); 6.90 (s, 2H); 8.19 (d, 2H, J=5.7Hz). MS (EI pos., 70 eV), m/z=387 ([M+]), 359 (100); 358 (85); 330 (20);28 (60).

[0276] This compound can also be obtained by heating pyrrolidine and4,4″-clichloro-1′H-[2,2′;6′,2″]-terpyridin-4′-one, if desired in thepresence of metal salts (see e.g. Example 6).

Example 254,4″-Bis[(2-hydroxy-ethyl)-methyl-amino]-1′H-[2,2′;6′,2″]terpyridin-4′-one(Referred to as L19 Below)

[0277]

[0278] This compound is prepared in a manner analogous to that describedin Example 6 for 4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, but instead2-(N-methylamino)ethanol is used as amine and4,4″-dichloro-1′H-[2,2′;6′,2″]terpyridin-4′-one from Example 22 is usedas precursor. ¹H-NMR (360 MHz, DMSO-d₆): 3.12 (s, 6H); 3.20-4.00 (m,8H); 6.73-6.82 (m, 2H); 7.70-7.95 (m, 4H); 8.23 (d, 2H, 5.9 Hz).

Example 26 4,4″-Diethoxy-4′-methoxy-[2,2′;6′,2″]terpyridine (Referred toas L20 Below)

[0279]

[0280] In an argon atmosphere, 506 mg (1.5 mmol) of4,4″-diethoxy-1′H-[2,2′;6′,2″]terpyridin-4′-one (L17, Example 23) areadded at 0° C. to a suspension of 78 mg (approximately 60% dispersion inparaffin oil, 1.95 mmol) of sodium hydride in 15 ml of absoluteN,N-dimethylformamide. The mixture is then stirred for 15 minutes at 0°C. and for 15 minutes at room temperature. After cooling again, 0.12 ml(1.95 mmol) of methyl iodide is added. Stirring is then carried out atroom temperature for a further 45 minutes. 15 ml of water are added andfiltration is carried out, yielding4,4″-diethoxy-4′-methoxy-[2,2′;6′,2″]terpyridine in the form of a beigepowder. ¹H-NMR (360 MHz, CDCl₃): 1.39 (t, 6H, J=7.2 Hz); 3.90 (s, 3H);4.12 (q, 4H, J=7.2 Hz); 6.73 (dd, 2H, J=5.6, 2.5 Hz); 7.88 (s, 2H); 8.01(d, 2H, J=2.5 Hz); 8.39 (d, 2H, 5.6 Hz). MS (EI pos, 70 eV), m/z=351(90, [M+]); 350 (70); 336 (100); 323 (70); 295 (45).

Example 27 4′-Methoxy-4,4″-di-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine(Referred to as L21 Below)

[0281] 26 mg of sodium hydride dispersion (60% strength, 0.65 mmol) aresuspended under argon in 5 ml of abs. N,N-dimethylformamide and cooledto 0° C. Then 193 mg (0.5 mmol) of4,4″-di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one (L18 fromExample 24) are added. The yellow suspension is stirred for 30 minutes0° C. and then heated at room temperature for 15 minutes. The mixture iscooled again and a solution of 40 μl (0.65 mmol) of methyl iodide isadded. The mixture is stirred for a further 45 minutes and theprecipitate that forms is filtered off and recrystallised from methanol.4′-Methoxy-4,4″-di-pyrrolidin-1-yl-[2,2′;6′,2″]-terpyridine is obtainedin the form of a white solid. 168.1 (quart.); 157.9 (quart.); 156.6(quart.); 152.9 (quart.); 149.5 (tert.); 107.4 (tert.); 107.1 (tert.);105.0 (tert.); 55.9 (prim.); 47.3 (sec.); 25.8 (sec.). MS (EI, 70 eV),m/z: 401 (50, [M+]); 373 (80); 372 (100); 332 (20); 28 (40).

Example 28 4,4′,4″-Trichloro-[2,2′;6′,2″]terpyridine (Referred to as L22Below)

[0282]

[0283] This compound is prepared in a manner analogous to that describedin Example 2 for 1′H-[2,2′;6′,2″]terpyridin-4′-one, but instead thedichloro-substituted pyridone L16 from Example 22 is used.4,4′,4″-Trichloro[2,2′;6′,2″]terpyridine, white solid. ¹H-NMR (90 MHz,CDCl₃): 7.24-7.31 (m, 2H), 8.38 (s, 2H); 8.45 (d, 2H, 1.8 Hz); 8.48 (d,2H, 5.0 Hz).

Example 29 4,4′,4″-Triethoxy-[2,2′;6′,2″]terpyridine (Referred to as L23Below)

[0284] 53 mg (0.15 mmol) of 4,4′,4″-trichloro[2,2′;6′,2″]terpyridinefrom Example 28 are added to 2.5 ml of a 0.72M ethanolic solution. Themixture is heated at reflux for 2 hours. The mixture is cooled, 2.5 mlof water are added and the 4,4′,4″-triethoxy[2,2′;6′,2″]terpyridine isfiltered off in the form of a pale pink powder. ¹³C-NMR (90 MHz, CDCl₃):167.4 (quart.); 166.2 (quart.); 158.4 (quart.); 157.1 (quart.); 150.7(tert.); 110.6 (tert.); 108.1 (2 signals, tert.); 64.2 (sec.); 64.1 (2signals, sec.); 15.0 (3 signals, prim.).

Example 30 4,4′,4″-Tri-pyrrolidin-1-yl[2,2′;6′,2″]terpyridine (Referredto as L24 Below)

[0285]

[0286] This compound is prepared in a manner analogous to that describedin Example 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thetrichloro-substituted terpyridine L22 from Example 28, and pyrrolidineas amine component are used.4,4′,4″-Tri-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, beige powder. MS(EI pos., 70 eV), m/z=440 (50, [M+]); 412 (80); 411 (100); 371 (20); 220(20), 28 (15). IR (cm⁻¹): 2850 (w); 1608 (vs); 1537 (s); 1515 (m); 1480(m); 1458 (m); 1019 (m); 799 (m).

Example 312-({4′,4″-Bis[(2-hydroxy-ethyl)methyl-amino]-[2,2′;6′,2″]terpyridin-4-yl}-methylamino)-ethanol(Referred to as L25 Below)

[0287]

[0288] This compound is prepared in a manner analogous to that describedin Example 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thetrichloro-substituted terpyridine L22 from Example 28, and2-methylaminoethanol as amine component are used.2-({4′,4″-Bis[(2-hydroxy-ethyl)-methyl-amino]-[2,2′;6′,Z′]terpyridin-4-yl}methyl-amino)-ethanol,white solid. ¹³ C-NMR (90 MHz, DMSO-d₆): 156.4 (quart.); 155.7 (quart.);155.3 (quart.); 154.4 (quart.); 149.2 (tert.); 106.7 (tert.); 103.4(tert.); 103.1 (tert.); 58.4 (2 signals, sec.); 58.2 (sec.); 53.6(sec.); 53.5 (2 signals, sec.); 38.6 (prim.); 38.3 (2 signals, prim.).

Example 32 4′-Chloro-4,4″-diethoxy-[2,2′;6′,2″]terpyridine (Referred toas L26 Below)

[0289]

[0290] This compound is prepared in a manner analogous to that describedin Example 2 for 1′H-[2,2′;6′,2″]terpyridin-4′-one, but instead thediethoxy-substituted pyridone L17 from Example 23 is used.4′-Chloro-4,4″-diethoxy-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 166.3 (quart.); 157.0 (quart.); 156.9 (quart.); 150.8(tert.); 146.5 (quart.); 121.7 (tert.); 110.8 (tert.); 108.4 (tert.);64.2 (sec.); 14.9 (prim.).

Example 33 4,4″-Diethoxy-4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine(Referred to as L27 Below)

[0291]

[0292] This compound is prepared in a manner analogous to that describedin Example 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thechloro-substituted terpyridine L26 from Example 32, and pyrrolidine asamine component are used.4,4″-Diethoxy-4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, white solid.¹³C-NMR (90 MHz, CDCl₃): 166.2 (quart.); 159.4 (quart.); 157.1 (quart.);155.6 (quart.); 150.4 (tert.); 110.5 (tert.); 107.9 (tert.); 104.8(tert.); 63.9 (sec.); 47.8 (sec.); 25.8 (sec.); 15.0 (prim.). MS (EIpos., 70 eV), m/z=390 (100, [M+]); 333 (70.); 305 (20); 28 (25).

Example 342-[(4,4″-Diethoxy-[2,2′;6′,2″]terpyridin-4′-yl)-(2-hydroxy-ethyl)-amino]-ethanol(Referred to as L28 Below)

[0293]

[0294] This compound is prepared in a manner analogous to that describedin Example 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thechloro-substituted terpyridine L26 from Example 32 is used as aminecomponent. Recrystallisation from methanol yields2-[(4,4″-diethoxy-[2,2′;6′,2″]terpyridin-4′-yl)-(2-hydroxy-ethyl)-amino]-ethanolin the form of a white solid. ¹³C-NMR (90 MHz, CDCl₃): 165.5 (quart.);158.0 (quart.); 155.0 (quart.); 154.6 (quart.); 150.6 (tert.); 110.4(tert.); 107.0 (tert.); 103.5 (tert.); 63.6 (sec.); 57.9 (sec.); 52.7(sec.); 14.5 (prim.).

Example 35 6,6″-Bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine (Referred toas L29 Below)

[0295]

[0296] A solution of 7.6 g (24 mmol) of caesium carbonate in 8 ml ofwater is added to a solution of 0.9 g (2.3 mmol) of6′,6″-dibromo-2,2′:6′,2″-terpyridine in 14 ml of dimethoxyethane. 8.9 mg(0.02 mmol) of μ-bromo(triisopropylphosphine)(η³-allyl) palladium(II)(see WO-A-99/47474) and 0.89 g (5.88 mmol) of 2-methoxyphenylboronicacid are added. The mixture is then heated at reflux under argon for 10hours. The mixture is cooled and the phases are separated; the organicextract is extracted three times with ethyl acetate. The organic phaseis dried over sodium sulfate, filtered and concentrated. The crudeproduct is chromatographed (silica gel, hexane/ethyl acetate 10:1).6,6″-Bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 157.7 (quart.); 155.7 (quart.); 155.3 (quart.); 138.2(tert.); 137.1 (tert.); 131.9 (tert.); 130.5 (tert.); 129.3 (quart.);125.6 (tert.); 121.6 (tert.); 121.5 (tert.); 119.5 (tert.); 112.0(tert.); 56.1 (prim.).

Example 36 6,6″-Bis(2-hydroxyphenyl)-2,2′:6′,2″-terpyridine (Referred toas L30 Below)

[0297] 1.12 g (4.49 mmol) of boron tribromide dissolved in 5 ml ofdichloromethane are added dropwise at −75° C. to a solution of 200 mg(0.448 mmol) of 6,6″-bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine (L29,Example 35) in 15 ml of dichloromethane. After one hour the cooling bathis removed and the solution is stirred at room temperature for 10 hoursto complete the reaction. The solution is poured into ice-water andneutralised with sodium hydrogen carbonate solution. Extraction iscarried out twice with dichloromethane and the combined organic extractsare dried over sodium sulfate, filtered and concentrated. The crudeproduct is chromatographed (silica gel, dichloromethane/methanol 20:1).6,6″-Bis(2-hydroxyphenyl)-2,2′:6′,2″-terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃):160.2 (quart.); 157.7 (quart.); 154.5 (quart.); 153.1(quart.); 139.4 (tert.); 139.2 (tert.); 132.1 (tert.); 130.2 (quart.);126.9 (tert.); 121.9 (tert.); 121.6 (tert.); 120.0 (tert.); 119.5(tert.); 119.2 (tert.); 118.9 (tert.).

[0298] Synthesis of Metal Complexes with Terpyridine Ligands and4-pyridone Ligands

Example 37 Manganese(II) Complex Containing a Pyridone Ligand:{[2,2′;6′,2″]terpyridin-4′-ol}manganese(II) chloride.

[0299] 198 mg (1 mmol) of manganese(II) chloride tetrahydrate aredissolved in 10 ml of ethanol, and 249 mg (1 mmol) of1′H-[2,2′;6′,2″]terpyridin-4′-one L1 are added. The mixture is stirredfor 24 hours at room temperature and filtered, and the light-yellowsolid is dried in vacuo.

[0300] C₁₅H₁₁Cl₂MnN₃O, 375.12; calculated C 48.03H 2.96 N 11.20 Mn14.65, found C 48.22H 3.14 N 11.13 Mn 14.6. IR (cm⁻¹): 3082 (br, vs),1613 (s), 1600 (s), 1558 (s), 1429 (m), 1224 (s), 1011 (m), 798 (m).

Example 38 Manganese(II) complex with a substituted terpyridine ligand:{2-[(2-hydroxyethyl)-[2,2′;6′,2′¹]terpyridin-4′-yl-amino]-ethanol}manganese(II)chloride

[0301] 336 mg (1 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7dissolved in 5 ml of water are added dropwise to 5 ml of an aqueoussolution of 198 mg (1 mmol) of manganese(II) chloride tetrahydrate. Themixture is then stirred for 20 minutes at room temperature and filtered,and the light-yellow solid is dried in vacuo.

[0302] C₁₉H₂₀Cl₂MnN₄O₂*0.11H₂O; calculated C 49.16H 4.39 N 12.07 Mn11.83, found C 49.23H 4.38 N 12.07 Mn 12.1. IR (cm⁻¹): 3512 (w), 3456(m), 1609 (vs), 1569 (w), 1518 (s), 1532 (w), 1569 (w), 1473 (w), 1444(s), 1055 (w), 1055 (s), 1013 (vs), 789 (vs).

Example 38a{2-(Methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol}manganese(II)Chloride

[0303] 7.66 g (25 mmol) of2-(methyl[2,2′;6′,2″]terpyridin-4′-yl-amino)ethanol L5 are added, infive portions, over a period of 30 minutes to 100 ml of an ethanolicmanganese(II) chloride tetrahydrate solution (4.95 g, 25 mmol). Themixture is diluted with 70 ml of ethanol, stirred for 18 hours at roomtemperature and filtered, and the light-yellow solid is dried in vacuo.C₁₈H₁₈Cl₂MnN₄O; calculated C 50.02H 4.20 N 12.96 Mn 12.71 Cl 16.41,found C 49.90H 4.12 N 12.78 Mn 12.9 Cl 16.33.

Example 39 Manganese(II) complex with two substituted terpyridineligands:bis{2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol}manganese(II)chloride

[0304] 336 mg (1 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2′]terpyridin-4′-yl-amino]-ethanol L7 aresuspended in 5 ml of ethanol/water, and an ethanolic solution of 99 mg(0.5 mmol) of manganese(II) chloride tetrahydrate is added. The mixtureis stirred at room temperature for 90 minutes and filtered, and theorange-yellow solid is dried. C₃₈H₄₀Cl₂MnN₈O₄*H₂O, calculated C 55.89H5.18 N 13.72 Mn 6.73, found C 56.08H 5.44 N 13.58 Mn 6.66. IR (cm⁻¹):3240 (br), 1598 (vs), 1570 (w), 1510 (m), 1473 (m), 1442 (s), 1046 (w),1011 (vs), 792 (w).

[0305] Modification of manganese-bonded, substituted terpyridine-likeligands, direct complex synthesis:

Example 40Bis{4,4″-bis[(2-hydroxy-ethyl)-methyl-amino]-[2,2′;6′,2″]terpyridin-4′-ol}-manganese(II)Chloride

[0306] 318 mg (1 mmol) of L16 are heated at reflux in 25 ml of methanolwith 426 mg (2.2 mmol) of manganese(II) chloride tetrahydrate and 8.8 g(117 mmol) of N-methylaminoethanol under argon for 18 hours. The mixtureis concentrated and the residue is chromatographed on silica gel(dichloromethane/methanol 4:1). C₄₂H₅₀Cl₂MnN₁₀O₆, yellow solid. IR(cm⁻¹): 3238 (br, m), 1603 (vs) 1511 (s), 1536 (m), 1484 (m), 1450 (m),1356 (w), 1010 (s).

[0307] Synthesis of higher valency manganese complexes with substitutedligands of the terpyridine type (Examples 41 to 44) [cf. process of J.Limburg et al., Science 1999, 283, 1524-1527 for terpyridine]:

Example 41

[0308] 1.78 g (7.14 mmol) of 1′H-[2,2′;6′,2″]terpyridin-4′-one L1 areadded to a solution of 1.75 g (7.14 mmol) of manganese(II) acetatetetrahydrate in 35 ml of water. Then a solution of 3.28 g (9.93 mmol ofactive oxygen as KHSO₅) of potassium peroxomonosulfate in 20 ml of wateris added dropwise thereto. The mixture is then stirred for 2 hours atroom temperature, then filtered with suction and washed with 25 ml ofwater. Drying is carried out for 12 hours at 50° C. in vacuo, yielding2.05 g of olive-green powder. IR (cm⁻¹): 3068 (m), 1613 (m), 1602 (m),1587 (s), 1480 (m), 1099 (vs), 1053 (w), 1028 (s), 1011 (s), 788 (m).

Example 42

[0309] 1.23 g (5 mmol) of manganese(II) acetate tetrahydrate are addedto a suspension of 1.68 g (5 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7. Asolution of 1.44 g (4.37 mmol of active oxygen as KHSO₅) of potassiumperoxomonosulfate in 30 ml of water is then added dropwise. To theresulting red solution there is then added dropwise a total of 25 ml of1M ammonium hexafluorophosphate solution. The precipitate is filteredoff and washed twice using 10 ml of water each time.

[0310] The red solid is then taken up in 30 ml of acetonitrile, filteredthrough a paper filter and concentrated. The residue that remains isextracted with dichloromethane for 16 hours in a Soxhlet apparatus andthen dried at 50° C. in vacuo. 2.15 g of wine-red powder are obtained.

[0311] IR (cm⁻¹): 2981 (s), 2923 (s), 2866 (m), 2844 (m), 1621 (s), 1571(w), 1537 (w), 1475 (s), 1356 (m), 1055 (s), 1032 (vs), 1011 (s), 829(vs), 784 (s), 740 (w).

Example 43

[0312] 99 mg (0.5 mmol) of manganese(II) chloride tetrahydrate are addedto a suspension of 168 mg (0.5 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7. Asolution of 144 mg (0.44 mmol of active oxygen as KHSO₅) of potassiumperoxomonosulfate in 3 ml of water is then added dropwise. The almostblack solid is filtered off and dried at 50° C. in vacuo. IR (cm⁻¹):3324 (br, m), 3076 (br), 1614 (s), 1523 (w), 1476 (m), 1154 (w), 0.1055(w), 1025 (vs), 925 (w), 647 (s).

APPLICATION EXAMPLES Application Example 1 Stability of the Mn Complexes

[0313] For this purpose, 50 μmolar aqueous solutions of a complex ofmanganese(II) chloride tetrahydrate and a terpyridine-like ligand,dissolved in a borax buffer of pH 10.0, are prepared.

[0314] For testing the stablity, the solutions are exposed at 40° C. toa hydrogen peroxide concentration of 8.6 mM for 30 minutes.

[0315] For comparison purposes, a corresponding solution of theunsubstituted terpyridine ligand is prepared (without-hydrogenperoxide).

[0316] The optical density is determined by means of the respectiveUV/VIS spectrum at the wavelength indicated in Table 1 below and is ameasure of the stability.

[0317] The Mn complex of formula (137) given in Table 1 below is thecompound of formula TABLE 1 (137)

Compound Time Optical density Unsubstituted terpyridine — 0.03 (335 nm)Mn complex (137) t = 0 min. 0.43 (335 nm) Mn complex (137) t = 30 min.(without H₂O₂) 0.11 (335 nm) Mn complex (137) t = 30 min. (with H₂O₂)0.08 (335 nm) Mn complex (134) t = 0 min. 0.60 (320 nm) Mn complex (134)t = 30 min. (without H₂O₂) 0.60 (320 nm) Mn complex (134) t = 30 min.(with H₂O₂) 0.60 (320 nm)

[0318] The above Example shows that the manganese complex withsubstituted terpyridine has markedly greater stability in comparisonwith the manganese complex with unsubstituted terpyridine. In the caseof the manganese complex with unsubstituted terpyridine, the complex haslargely decomposed after 30 minutes, and the UV/VIS spectrum obtained isvirtually the same as that of the ligand (terpyridine), whereas themanganese complex with the substituted terpyridine is stable.

Application Example 2 Bleaching Action in Washing Agents

[0319] 7.5 g of white cotton fabric and 2.5 g of tea-stained cottonfabric are treated in 80 ml of washing liquor. The liquor contains astandard washing agent (ECE, 456 IEC) in a concentration of 7.5 g/l. Thehydrogen peroxide concentration is 8.6 mmol/l. The catalystconcentration (1:1 complex of manganese(II) chloride tetrahydrate withthe ligand in question, prepared in methanolic solution with theaddition of a small amount of lithium hydroxide) is 50 μmol/l. Thewashing process is carried out in a steel beaker in a LINITEST apparatusfor 30 minutes at 40° C. For evaluating the bleaching results, theincrease in the lightness DY (difference in lightness according to CIE)of the stains brought about by the treatment is determinedspectrophotometrically in comparison with values obtained without theaddition of catalyst. TABLE 2 1:1 Mn complex with ligand DY increaseLigand DY increase L1 5.0 L10 4.4 L4 5.0 L11 5.5 L5 5.2 L17 5.3 L6 5.8L18 3.0 L7 5.6 L19 5.3¹⁾ L8 5.0 L25 6.2 L8a 4.5 L28 4.3 L9 3.8

[0320] As can be seen from Table 2 above, the manganese complexesexhibit a very good bleaching action.

Application Example 3 Cleaning Performance on Soiled Surfaces at 53° C.

[0321] A tea-stained cup is filled with 100 ml of a buffer solution (10mM carbonate, pH=10.0) containing 1.1 mM of hydrogen peroxide and 7.3 μMof 1:1 manganese complex (prepared as described in Application Example2). Using a thermostat, the temperature of the solution is raised from23° to 53° C. over a period of 12 minutes and maintained at the finaltemperature for 23 minutes. After rinsing and drying in air, the resultsare evaluated visually on a scale of 1 (no cleaning) to 10 (clean). Thecatalyst-free system is used as reference. TABLE 3 1:1 Manganese Rating(rating of complex with ligand reference) Difference L1 5.0 (3.1) 1.9 L67.2 (3.3) 3.9 L7 6.9 (3.3) 3.6 L10 5.2 (3.1) 2.1 L11 5.7 (3.3) 2.4 L285.2 (3.0) 2.2 Unsubstituted 3.8 (3.9) −0.1 terpyridine

Application Example 4 Cleaning Performance on Soiled Surfaces at 23° C.

[0322] The procedure is as in Application Example 3 but the cleaning iscarried out at a constant temperature of 23° C. (duration: 45 minutes).TABLE 4 Rating (rating of Compound used reference) Difference Manganesecomplex of formula 7.6 (3.8) 3.8 (136) N,N′-tetraacetylethylenediamine6.8 (3.9) 2.9 (TAED), 0.16 g/l

Application Example 5 Decomposition of Hydrogen Peroxide

[0323] The procedure is as in Application Example 3 but the consumptionof H₂O₂ is determined iodometrically. TABLE 5 1:1 manganese complex withligand Residual H₂O₂ (mM) Consumption (%) L1 0.73 34 Unsubstitutedterpyridine 0.02 98

[0324] As can be seen in Table 5, in the case of the use of the 1:1manganese complex with the substituted terpyridine ligand the undesireddecomposition of H₂O₂ to O₂ and H₂O is substantially reduced.

Application Example 6 Activity of the Manganese Catalysts After theBleaching Cycle

[0325] The procedure as described in Application Example 2 is carriedout for the 1^(st) cycle, the cotton fabric is removed and for the2^(nd) cycle the procedure is carried out afresh with a new, as yetuntreated cotton fabric. The DY values are determined as described inApplication Example 2. TABLE 6 Bleaching value Bleaching value with H₂O₂with H₂O₂ and the (without Mn 1:1 Mn complex Difference complex) withthe ligand L7 DDY 1^(st) cycle DY = 14.9 DY = 23.0 8.1 2^(nd) cycle DY =11 DY = 19.0 8.0

[0326] As can be seen from Table 6, the liquors comprising the manganesecomplex can be used for further bleaching cycles without any appreciablereduction in the bleaching action.

Application Example 7 Catalytic Bleaching of Cellulose

[0327] 20 g of cellulose [TPP-CT CSF129, Ref. No. P-178635 (ISO 57.4)]are steeped in a litre of water for 65 hours and then stirred in a mixerfor 2 minutes to give a paste-like pulp.

[0328] A bleaching bath containing 50 g of the pulp so prepared in 180ml of water, 100 μM of Dequest 2041 (sequestering agent), 8.6 mM ofhydrogen peroxide and 20 μM of catalyst from Example 35 is maintained at40° C. for 30 minutes. At the same time 1 N sodium hydroxide solution ismetered-in in such a manner that a pH of 10.0 is maintained. Filtrationand air-drying are then carried out. A sample that has been compressedto form a circular sheet of 10 cm diameter is then tested for thelightness Y obtained (according to CIE, reflectance spectroscopy). Theresults are compiled in the following Table. TABLE 7 Lightness Y Testsample, untreated 63.4 Test sample, catalytically bleached 66.9

Application Example 8 Action as Catalyst for DTI (Dye TransferInhibition)

[0329] In accordance with this application, the redeposition of dyes inwashing liquors, especially, should be avoided.

[0330] 7.5 g of white cotton fabric are treated in 80 ml of washingliquor. The liquor contains a standard washing agent (ECE, 456 IEC) in aconcentration of 7.5 g/l. The hydrogen peroxide concentration is 8.6mmol/l. The catalyst concentration (of manganese(II) chloridetetrahydrate with the ligand, prepared in methanolic solution with theaddition of a small amount of lithium hydroxide) is 50 μmol/l, and asolution of the test dye Direct Brown 172 having 10 mgA of the 250%formulation. The washing process is carried out in a steel beaker in aLINITEST apparatus for 30 minutes at 40° C. For testing the activity ofthe catalysts, the DTI activity is determined. The DTI (Dye TransferInhibition) activity a is defined as the following percentage.

a=([Y(E)−Y(A)]/[Y(W)−Y(A)])·100

[0331] where Y(WV), Y(A) and Y(E) are the CIE lightness values of thewhite material, of the material treated without the addition of catalystand of the material treated with the addition of catalyst, in thatorder. a=0 denotes a completely inactive product, the addition of whichto the washing liquor does not prevent dye transfer, whereas a=100%corresponds to a perfect catalyst which totally prevents the staining ofthe white material.

[0332] The reflection spectra of the samples were measured using aSPECTRAFLASH 2000 and converted into lightness values (D65/10) inaccordance with a standard CIE procedure.

[0333] A 1:1 manganese complex with ligand L7 gives a value of a=90% inaccordance with the test procedure described above.

[0334] Application Example 9: The use of the catalysts according to theinvention causes hardly any additional fading of the dyes in dyed cottonlaundry. When used as described above in Application Example 8, aftertreatment five times, on average, virtually no losses of dye arerecorded. The values given in the following Table are relativepercentage dye losses, determined on the basis of Kubelka-Munk values atthe respective absorption maximum. TABLE 8 Dye loss (%) in system Cottondyeing with dye with Mn-L7 (50 μM) without catalyst Cibanone Brown BR 00 Cibanone Blue RS 3 2 Procion Brown H-4RD 9 11 Levafix Scarlet E-2GA 1010

Application Example 10 Catalytic Action for the Epoxidation of Olefins

[0335] 17 mg (0.05 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol (L7,Example 7), 10 mg (0.04 mmol) of manganese(II) acetate tetrahydrate and0.32 mmol of sodium ascorbate are added to a solution of 1.09 ml (10mmol) of ethyl acrylate in 0.5 ml of acetonitrile. The mixture is cooledin an ice bath and a 30% strength hydrogen peroxide solution (2.27 g, 20mmol) is added dropwise thereto in the course of 20 minutes. The mixtureis then left for 14 hours at room temperature, then diluted with diethylether and the phases are separated. The organic extract is dried oversodium sulfate, filtered and concentrated. The catalytic turnover numberfor the epoxide formed, ethyl oxirane-2-carboxylate, is determined bycomparing the intensity of the epoxide methine proton at 3.34-3.38 ppmwith the ligand signal L7 at 8.53 ppm as reference and is 35±8. Ethyloxirane-2-carboxylate, epoxide signals ¹H-NMR (360 MHz, CDCl₃):2.68-2.89 (m, 2H, CH₂); 3.34-3.38 (m, 1H, CH). Without the addition ofligand, epoxide cannot be detected.

[0336] (see in this connection also Berkessel, A. et al., TetrahedronLett. 1999, 40, 7965-7968).

What is claimed is:
 1. Use of a metal complex compound of formula [L_(n) Me _(m) X _(p)]^(z) Y _(q)  (1), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8, p is an integer having a value of from 0 to 32, z is thecharge of the metal complex, Y is a counter-ion, q=z/(charge Y), and Lis a ligand of formula

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are eachindependently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or aryl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ whereinR₁₂ is in each case hydrogen, a cation or unsubstituted or substitutedC₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each casehydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or substituted 5-, 6- or 7-memberedring which may optionally contain further hetero atoms; with the provisothat R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are notsimultaneously hydrogen, as a catalyst for oxidation reactions.
 2. Useaccording to claim 1, wherein Me is manganese which is present inoxidation state 11, III, IV or V.
 3. Use according to either claim 1 orclaim 2, wherein X is CH₃CN, H₂O, F, Cl⁻, BrC, HOO⁻, O₂ ²⁻, O²⁻,R₁₇COO⁻, R₁₇07, LMeO or LMeOOr wherein R₁₇ is hydrogen or unsubstitutedor substituted C₁-C₁₈alkyl or aryl, and L and Me are as defined inclaim
 1. 4. Use according to any one of claims 1 to 3, wherein Y isR₁₇COO⁻, ClO₄ ⁻, BF₄′, PFe⁻, R₁₇SO₃ ⁻, R₁₇SO₄ ⁻, SO₄ ², NO₃′, F⁻, Cl⁻,Br or I— wherein R₁₇ is hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl.
 5. Use according to any one of claims 1 to 4,wherein n is an integer having a value of from 1 to 4, especially 1 or2.
 6. Use according to any one of claims 1 to 5, wherein m is an integerhaving a value of 1 or 2, especially
 1. 7. Use according to any one ofclaims 1 to 6, wherein p is an integer having a value of from 0 to 4,especially
 2. 8. Use according to any one of claims 1 to 7, wherein z isan integer having a value of from 8− to 8+.
 9. Use according to any oneof claims 1 to 8, wherein aryl is phenyl or naphthyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl,sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁C₄alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy.
 10. Use according toany one of claims 1 to 9 wherein the 5-, 6- or 7-membered ring formed byR₁₄ and R₁₅ together with the nitrogen atom bonding them is anunsubstituted or C₁-C₄alkyl-substituted pyrrolidine, piperidine,piperazine, morpholine or azepane ring.
 11. Use according to any one ofclaims 1 to 10, wherein R₆ is C₀-C₁₂alkyl; phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl,sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; cyano; halogen; nitro;—COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N″R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂-alkyl, or phenyl unsubstituted orsubstituted as indicated above, or R₁₄ and R₁₅ together with thenitrogen atom bonding them form an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring; and R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁, are asdefined above or are hydrogen.
 12. Use according to claim 11, whereinthe ligand L is a compound of formula

wherein R′₃, R′₆ and R′₉ are as defined for F? in claim
 11. 13. Useaccording to claim 12, wherein R′₃, R′₆ and R′₉ are each independentlyof the others C₁-C₄alkoxy; hydroxy; phenyl unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, phenyl or by hydroxy; hydrazino; amino;N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety; or an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.
 14. Use according to claim 13, wherein R₆ is hydroxy.15. Use according to any one of claims 1 to 14, wherein a metal complexcompound of formula (1) is used in a washing, cleaning, disinfecting orbleaching agent.
 16. Use according to claim 15, wherein a metal complexcompound of formula (1) is formed in situ in the washing, cleaning,disinfecting or bleaching agent.
 17. Use according to any one of claims1 to 16, wherein a metal complex compound of formula (1) is usedtogether with a peroxy compound for the bleaching of spots or stains ontextile material or for the prevention of the redeposition of migratingdyes in the context of a washing process or for the cleaning of hardsurfaces.
 18. Use according to any one of claims 1 to 15, wherein ametal complex compound of formula (1) according to claim 1 is used as acatalyst for reactions with a peroxy compound for bleaching in thecontext of paper-making.
 19. Use according to any one of claims 1 to 14,wherein a metal complex compound of formula (1) is used as catalyst forselective oxidation reactions in the context of organic synthesis.
 20. Ametal complex compound of formula [L _(n) Me _(m) X _(p)]^(z) Y_(q)  (1a), wherein Me is manganese, titanium, iron, cobalt, nickel orcopper, X is a coordinating or bridging radical, n and m are eachindependently of the other an integer having a value of from 1 to 8, pis an integer having a value from 0 to 32, z is the charge of the metalcomplex, Y is a counter-ion, q=z/(charge Y), and L is a ligand offormula

wherein R is unsubstituted or substituted C₁-C₁₈alkyl; cyano; halogen;nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cationor unsubstituted or substituted C₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen or unsubstituted orsubstituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ andR″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or —N′R₁₄R₁₅R₁₆ wherein R₁₄,R₁₅ and R₁₆ are each independently of the other(s) hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orsubstituted 5-, 6- or 7-membered ring which may optionally containfurther hetero atoms; and R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉. R₁₀ and R₁₁are each independently of the others as defined above for R₆ or arehydrogen or unsubstituted or substituted aryl, with the proviso thatwhen Me is titanium, iron, cobalt, nickel or copper, R₃ and R₉ are nothydrogen and the three radicals R₃, R₆ and R₉ do not have identicalmeanings.
 21. A metal complex compound according to claim 20, wherein Meis manganese which is present in oxidation state II, III, IV or V.
 22. Ametal complex compound according to either claim 20 or claim 21, whereinthe ligand is a compound of formula

wherein R′₆ is C₁-C₁₂alkyl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂wherein R₁₂ is in each case hydrogen, a cation, C₁-C₁₂alkyl, or phenylunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano,nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or bynaphthoxy; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholine or azepane ring; and R′₃and R′₉ are as defined above or are hydrogen or phenyl unsubstituted orsubstituted as indicated above.
 23. A compound of formula

wherein R is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is ineach case hydrogen, a cation or unsubstituted or substituted C₁-C₁₈alkylor aryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl,or R₁₄ and R₁₅ together with the nitrogen atom bonding them form anunsubstituted or substituted 5-, 6- or 7-membered ring which mayoptionally contain further hetero atoms; and R₁, R₂, R₃, R₄, R₅, R₇, R₈,R₉, R₁₀ and R₁₁, are each independently of the others as defined abovefor R₆ or are hydrogen or unsubstituted or substituted C₁-C₁₈alkyl oraryl, with the proviso that the three radicals R₃, R₆ and R₉ do not haveidentical meanings.
 24. A compound according to claim 23 of formula

wherein R′₆ is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ isin each case hydrogen, a cation, C₁-C₁₂alkyl, or phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl,sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; —SR₁₃, —O₂R₁₃ or —OR₁₃wherein R₁₃ is in each case hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen, unsubstituted or hydroxyl-substituted C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring; and R′₃ and R′₉ are as defined above or are hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above.25. A washing, cleaning, disinfecting or bleaching agent, comprising I)0-50% A) of an anionic surfactant and/or B) of a non-ionic surfactant,II) 0-70% C) of a builder substance, III) 1-99% D) of a peroxide, andIV) E) a metal complex compound of formula (1) in an amount which, inthe liquor, gives a concentration of 0.5-50 mg/litre of liquor,preferably 1-30 mg/litre of liquor, when from 0.5 to 20 g/litre of thewashing, cleaning, disinfecting and bleaching agent are added to theliquor, the percentages in each case being percentages by weight, basedon the total weight of the agent.
 26. A solid preparation, comprising a)from 1 to 99% by weight of a metal complex compound according to claim20; b) from 1 to 99% by weight of a binder; c) from 0 to 20% by weightof an encapsulating material; d) from 0 to 20% by weight of a furtheradditive; and e) from 0 to 20% by weight of water.
 27. A solidpreparation according to claim 26 which is in granular form.